Benzoylacet-o-alkoxyanilide couplers for color photography



' Feb. 24, 1959 OPT/CAL DENSITY D A Q: Q N

F. c. MCCROSSEN ETAL 2,875,057 BENZOYLACET-O-ALKOXYANILIDE COUPLERS FOR COLOR PHOTOGRAPHY Filed March so, 1956 ABSORPT/O/VS OE DYES MADE FROM.

coo/1 COIVH c H 82 O I 2 C0 HCON A/Hc0c/1 0 OC H O 2 O I l l 1 T I 1 400 500 20 40 60 80 600 20 40 60 80 700 WA VE LENGTH //V M/LL lM/CRO/VS FRED v 6.- M CROSSE/V PAUL M. WTTUM ARNOLD WE/SSBERGER INVENTORS ATTORNEY H AGE/VT BENZOYLACET-o-ALKOXYANILIDE COUPLERS FOR COLOR PHOTOGRAPHY Fred C. McCrossen, Paul W. Vittum, and Arnold Weissberger, Rochester, N. Y., assignors to Eastman Kodak;

Company, Rochester, Jersey Application March 30, 1956, Serial No. 575,099 10 Claims. (Cl. 96-100) N. Y., a corporation of New o 01-120 ONE-mg wherein R represents an alkyl group of from 1 to 20 carbon atoms and either one of the groups X and Y represents a hydrogen atom and the other represents an acylamido group.

A particularly eflicacious group of the coupler com,

pounds of the invention have the above general formula.

wherein either one of the groups X and Y represents a hydrogen atom and the other represents the group CtHu wherein R represents a hydrogen atom or an alkyl group of from 1 tow4 carbon atoms, Thesecompounds are illustrated by Compounds I to V, X, XIV and XV hereinafter.

A distinctive feature of the coupler compounds having the above formulas residesjn. the; presence of the; alkoxyl group in the ortho position of only the anilide nucleus.

2,875,057 Patented Feb. 24, 1959 ICE That is, alkoxybenzoylacetanilide having the formula couplers are known 0 OCHzOONHR" are shown byWeissberger et al. U. 8.. Patent 2,407,210, September 3, 1946, and similar alkoxylated couplers having the formula are shown by U. S. Patent 2,678,882. It will be apparent from these last two formulas that the couplers of the patents always contain an alkoxyl group in the ortho position of the benzoyl nucleus and in the latter formula there is also present an alkoxyl group in the ortho position of the anilide group.

We have discovered that if the benzoylacetanilide coupler compounds contain an alkoxyl group of from about 1 to 20 carbon atoms in the ortho position of the anilide group but contain no alkoxyl group on the benzoyl group but do contain an acylamido group attached directly to either the benzoyl or the anilideigroup of the coupler, as in the first general formula above, the coupler compounds possess properties separate and distinct from the coupler compounds of the mentioned. patents.

The accompanying drawing illustrates the distinctive features of the compounds of the invention. In the drawing are shown the absorption curves 1, 2 and 3 of dyes obtained by development of a silver halide emulsion with a primary aromatic amino silver halide developer in the presence of the compounds 1, 2 andl 3 having the structures shown in the legend of the drawing. A comparison of curves 1 and 2 shows that the effect of the introduction of the methoxyl group in the ortho position of the benzoyl group of compound 1 to obtain compound 2, is to shift the whole absorption curve toward the shorter wave lengths without altering its shape or sharpness of absorption. However, when the methoxyl group is introducedinto the ortho position of only the anilide group as in compound 3 of the invention, as shown in curve 3, the absorption maximum is not shifted appreciably but the sharpness of absorption is increased as shown, by the increased gradient of curve 3 compared to curves 1 and 2. Accordingly, this results in a distinct reduction in green light absorption of the yellow dye without effectively changing the blue light absorption of the dye. Similar results can be expected when a comparison is made of the coupler compounds of the invention with other known alkoxylated couplers, for example, of U. 8 Patent 2,678,882, having alkoxyl groups on both the benzoyl and anilide nuclei of the benzoylacetanilide couplers.

The following table illustrates the couplers ofthe in vention having the above general formulas:

ple'i conip'ounds" of the invention having the general fore 40 ml. (0.22 mole) o'f ethyl b'enioy'l acetate was f'ornillilzi" above are" illustrated by Compounds I to V added. About 9 ml. of distillate wa's collected in two an'cl'XIV having the structures hours. The brown solution was filtered from mechanical (U impurities and allowed to stand at room temperature M overnight. The precipitate wasfiltered, Washed with 100 Q Q m1. of xylene, washed with mom. of petroleum ether,

6 I 26 slurried with 200 m1. of denatured alcohol; and dried up can) t The yield was 39 g. (62%) of a yellow solid which 4-henzoylacetamido-3-methoxy;(2',4'-dl-tertamylphenoxy)- melted at 79 1 0 c 11 acetamhde at B l 4-amin" 2 methox acet nilid I draclilo- (It) NHCOQHCzHS 0 y a 8 1y rid.-In a; one-liter 3-necked flask equipped with arecondenser were placed 31.4 g. (0.1 moleloflqf ben2oy1-2-metho'xy 4-nitroacetanilide, 200 ml of 50% aqueous denatured alcohol, and 150 m1. of glacial acetic acid. The mixture was brought to a boil, theheat was rernoved, and 31.4 g. of iron powder was added as rapidlyhs possible. When the initial reaction had subsided, heat was again applied and the reaction mixture otmc'domeom a =methxyacetamnde diluted as rapidlyaspossible with one liter of water and (III) Nficocmdpdmnm 300ml. of concentrated hydrochloric acicl. The'solution i 4o changed from a. deep brown to a deep yellow. After n m G 63 chilling overnight at 5 C., the hydrochloride was filtered, washed well with 500 ml'. of 5% hydrochloric 1 (77 of an off-wite soli was obtained w i ch turric'd 3-benzoylacetamlno-4 mti t llieoti rls (1126:? d1 tart amylphenoxy) red-in p s w. 1500 g. p 200 and :9 riielted with decomposition at 206-209 C, 4 5 berizoylacetamido' 3 met/10x3 (2,4' dz" teft- L a myl ihenoxy)acetunilid. -In a SOD-nil. Erlenmeyer Q' E flask equippedwith a stirrer were placed 16 g. (0 .05

mole) of abenz oyl-4-amino-2-niethoxyacetanilide hydrochloride and 10 g; (0.1+ mole) ofanhydrous sodium mthoxyacetann e acetate in 200 ml. of glacial acetic acid. With good 05Hn--C -0OILC'ONHOCOOEC-ONBFQ JtHu OCH};

-t- -i y p y) M I YU stirring 16 g. (0.051 mole) of 2,4-di-tert-arnylphenoxymethoxyacetanihde acetyl chloride were added After stirring at room tern- (X'W) O d peratur e for one hour, the reaction mixture was heated C2\H5 to 60 C. for one-half hour, cooled, and poured with {fib la} 'H O H O very vigorous stirring into tWo liters of cold water. After stirring until the precipitate was filter-able, the solid was climb) filtered, washed with 500 ml. of water, and sucked as a 1.. l dry as possible The moist solid was recrystallized from 2,441 -t- 1 h n b t 1d 1: 1-2- a {3 [a l n le in xgiggta inlici 0] enzoy} 5-10 parts of denatured alcohol to glve 16.3 g. (58.4%)

The coupler coinpounds provided above for'ill ustration of White material which melted Q 5f our invention can be prepared as follows:

Example 2 Examgle 1 Coupler No. His preparedas follows: Coupler No. I is prepared as follows: a Brizojzlf- 5- [cc (2,4 dz tert. LQI7ZylphliOxy) a-Benzoyl-2-nti2thoxy-4-nitroacetariilidahi a 250 ml. but'yrd'mia'o]=2rhe171oxyricetm'zilitz'ewJn a- 1 liter Erlenr'ound-bottom flask equipped with 21 partial condensing me'yer flask equipped with a stirrer ispla'ced 500 mltof stillhead were placed 33 6 g. (0.2 niole) of Z-nie'thoXY- glacial acetic acid, 20 g. of anhydrous sodium acetate, i fiit'roaniline" (Ber. 1'3", 390) and iiilkof histological 75 and 32 .1 g. of women-5muno=2qnernoxyacetaniude (as the hydrochloride) (Example 3). After stirring minutes, 33.9 g. of a-(2,4-di-tert.-amylphenoxy)- n-butyryl chloride is added all at once. The reaction mixture isstirred overnight at room temperature, drowned in 34 liters of cold water, and stirred until the precipitate is filterable. The tan product is filtered, washed well with water, and dried. The amorphous solid is recrystallized from 10-15 parts of methyl alcohol to yield 33 g. (56%) of white product which sinters at 72 C. and melts at 135-137 C., but occasionally contains alcohol of solvation and melts at 75-78 C.

Analysis.-Product M. P. 135137 C. Calc.: C,

73.8; H, 7.85; N, 4.8. Found: C, 73.6; H, 7.9; N, 4.8.

Example 3 Coupler No. III is prepared as follows:

, a-Benzoyl-Z-methoxy-Smitroacetanilide.--In a 250-ml. round b'ottom flask equipped with a partial condensing still-head were placed 100 ml. of histological xylene, and 16.8 grams (0.1 mole) of 4-nitro-2-aminoanisole (Ber. 13, 389). grams (0.1 mole) of ethyl benzoylacetate was added all at once. After refluxing 2 hours, about 3-5 ml. of ethyl alcohol had been collected. The yellow solution was filtered hot and allowed to-cool to room temperature. The yellow solid which separated wasfiltered, washed with 50 ml. of xylene, and finally with 100 ml. of petroleum ether. A crude yield of 26 grams (83 percent) was obtained which melted at 1707-175 C. On recrystallization from 18 pa'rtsof glacial acetic acid, 22.4 grams (71 percent) of fine light yellow needles, M. P. 177-179 'C., was obtained.

. a-Berzz0yl-5-amin0-2-meth0xyacetanilide.--In a Parr hydrogenation bottle were placed 16 grams (0.051 mole) of a-benzoyl-2-methoxy-5-nitroacetanilide, 250 ml. of absolute ethyl alcohol, and- 2-5 grams of Raney nickel. The reaction mixture was shaken under 2-3 atmospheres 'of'hydrogen overnight at room temperature. The nickel was removed by filtration and the filtrate cooled in an ice bath. The light yellow solid was filtered, washed with 50 ml. of cold methyl alcohol, and dried. The yield was 13 grams (90 percent) of a solid which melted at 108-110 C. V

3 benzoylacetamino 4 methoxy (2,4 di tertamylphenoxy)-acetanilide.ln a 250-ml. Erlenmeyer flask were placed 5.68 grams (0.02 mole) of a-benzoyl- 5-amino-2-methoxyacetanilide, 2 grams (002+ mole) of anhydrous sodium acetate, and 100 ml. of glacial acetic acid. With good stirring 6.2 grams (0.02'mole) of 2,4- 'di-tert-amylphenoxyacetyl chloride in ml. of glacial acetic acid was added all at once. The reaction mixture was stirred 1 hour at room temperature and V2 hour at 60 C. After cooling to room temperature, the reaction mixture was poured with vigorous stirring into 1 liter of cold water. The moist solid was filtered, washed with cold water, sucked as dry as possible, and recrystallized from 200 ml. of denatured alcohol. The yield was 7.5 grams (67 percent) of a tan powder which melted at 124-126 C. Recrystallization from 200 ml. of alcohol gave 6.2 grams (55%) of a product which melted at 132-134" C. I

The couplers isomeric to I and III are prepared similarly from the isomeric u-benzoyl methoxynitroacetanilides.

' Example 4 CouplerNo. 1V is prepared as follows:

e-(m-Nitrobenzoyl)-2-methoxyacetanilide.--To a refluxing mixture of 22 g. (093 mole) of ethyl a-(mmitrobenzoyl)-acetate (Biilow and Hailer, Ber. 35, 915 (1902)) in 150 ml. of histological xylene was added in one portion 11 g. (.09mole) of o-anisidine. The mixture was heated at the reflux temperature (oil bath at 1,45.55 C.) for two hours under a steam-jacketed stillhead, which permitted the removal of the alcohol-xylene The mixture was brought to a boil and 19.2

azeotrope. The product which separated from the cooled reaction mixture was filtered and sucked dry on a Bitchner funnel; the yield of yellow product was 24 g. (82% M. P. 1667 C.

a-(m-Aminobenzoyl)-2-methoxyacetanilide.-In a 5- liter, three-necked flask, equipped with, stirrer, reflux condenser and addition tube, are placed 104 g. of technical-grade sodium sulfide (0.8 mole) and 200 ml. of water. The mixture is stirred gently on a steam bath'until solution is complete, and 3200 ml. of ethyl alcohol is added. The mixture is boiled and 126 g. (0.4 mole) of a-(m-nitrobenzoyl)-2-methoxyacetanilide is added portionwise over a period of fifteen minutes with good stir: ring. The brown reaction mixture is heated at the boil ing point for one-half hour and poured on about an equal volume of ice. To the cold solution is added 212 g. (4 moles) of solid ammonium chloride. The mixture is stirred manually until the ammonium chloride is ,dissolved, and allowed to stand for forty minutes. The product is' filtered by suction and washed on the funnel with several liters of water, until the washings are colorless. The pale-yellow product is dissolved in 1600 ml. of boiling alcohol and 100 ml. of hot water added. A small amount of Darco is added, and the solution is filtered while hot. The cooled filtrate yields 89.1 g. (78.5%) of flufly yellow product, M. P. 139.5-40 C.

a-{S [0c (2,4 di tert amylphenoxy)acetamido] berzzoyl} 2 methoxyacetanilide.ln a SOO-cc. three necked flask, provided with a stirrer and thermometer, were placed 300 cc. of percent acetic acidand 30 g. (0.36 mole) of anhydrous sodium acetate. To this solution, at room temperature, was added 32.0 g. (0.1 mole) of a-(m-aminosbenzoyl)-2-methoxyacetanilide hydrochloride, an easily stirrable mixture resulting as the temperature dropped 2 C. After this mixture had been stirred for one-half hour, 37 g. (0.19 mole) of 2,4-di-tert-amylphenoxyacetyl chloride (see above) was added during approximately one-half minute. The reaction mixture became much thinner, but failed to clear up as the temperature rose from 25.5 C. to 33.5 C.; color was a pinkgray. Following one and one-half hours of stirring, the mixture was diluted dropwise over a period of one-half hour with 30 cc. of water and seeded with coupler. Further stirring overnight caused separation of product as a finely divided white mass.

The reaction mixture was drowned with stirring during fifteen minutes in 600 cc. of water, the product separating in white granules. Stirring was continued for forty-five minutes and the mixture filtered readily through a 5-inch Biichner funnel. The white solid was washed on the funnel with 2 liters of water, not over 20 C. Immediately, when the cake was no longer covered by water, it shrank in a characteristic manner away from the edge of the funnel as though threatening to become gummy. This change failed to occur as the cake was sucked and pressed thoroughly. The solid, which could be broken up easily, was air-dried, 60 g. being obtained; it had an indistinct melting range, starting at about C Twelve hundred cc. of cyclohexane was heated to a boil on the steam bath and the 60 g. of crude product dissolved therein, forming a pink solution. It was treated with 2 g. of Darco and the solution filtered hot through 2 g. of Darco on a 4-inch Biichner funnel. Clear filtrate was only slightly less colored than prior to the Darco treatment. The couplerwas permitted to crystallize undisturbed overnight. It was filtered readily, washed on the funnel with three -cc. portions of fresh cyclohexane. The yield was 47 g. (82% of the theoretical amount) of white coupler, which melted at 126-427" C.

, Exam-pie 5 liter flask fitted with a steam-jacketed column containing a downward water-cooled condenser were placed 73.8 g.

r assaosa (p-Aminobenzoyl)-2-methoxyactanilid.-In a Parr low-pressure hydrogenationapparatus 15.7 g; (0.05 mole) of"wp-nitrobenzoyl-2-methoxyacetanilide in 250 ml. of ethylaeetate isshakenat room temperature with Raney nickel under 38.5 p. s. i. of hydrogen. The theoretical amountof hydrogen is absorbedin 1 /2 hours. Thenickel removed by filtration and the filtrate is concentrated to dryness invacuo. The residue is crystallized from 500ml. of;methyl alcohol to give 9 g. (64%) of needles meltingat 134-136 C.

ob-{4- [oc-(2,4 di-tert amylphenoxy acetamido] benzyl}- Z-jmthoxyacetanilida-Jn a 4-1. beaker were placed 145 g., (0.51 mole) of u-(p-arninobenzoyl)-2-methoxyacetanilide,.50 g. (0.61mo1e) of anhydrous sodium acetate, and1.5l. of glacial acetic acid. The mixture was stirred vigorouslywhile 158 g. (0.51 mole) of 2,-4-di-tert-amylphenoxyacetyl chloride was added in one portion. Stirring was continued for three 'hours' before the crystalline product was collected. It was washed with 2 x 100-cc. portionsof glacial acetic acid and 2 x 500-cc. portions ofwater to give pale yellowplates, M. P. 154-156 C. Recrystallization from 2.5 l. of absolute ethanol gave 124 g. (44% of light yellow pIates M. P. l55-l57 C. Fhe couplers isomeric to IV andV are prepared in asimilar manner from. the isomeric u-nitrobenzoyl-2- methoxyacetanilides.

Example 6 C-ouplerNo. VIis prepared as follows: u (4-nitr0benz0yl)-2-0ctadecyloxyacetanilide.-A mixture of 36.1 g. (0.10 mole) of Z-octadecyloxyaniline and 23.7g. (0.10 mole) of ethyl a-(4-nitrobenzoyl)acetate was heatedfor 1 /2 hours in 200ml. of boiling xylene under a steam-jacketed stillhead which permitted the removal of the xylene-alcohol azeo trope. The mixture was filtered hot and chilled. The bright yellow product was filtered, washed with methanol and dried; yield 41 g. (74%),MIP'I 80 81 C.

a (4 aminobertzoyl) 2 octadcyloxyactanilidaa-(4-nitrobenzoyl)-2-octadecyloxyacetanilide (32 g., .058 mole) was suspended in boiling 90% acetic acid, and 32 g of"iron-powderwasadded cautiously. The reaction mixture was filtered, and the filtrate drowned in water (3 1;). The solid was-filtered and washed with -10% acetic acid. Thecombined products of two such runs were recrystallized from 95% ethanol. The total yield based on 641 g; of starting material was 56 g. (86%), M. P. 83-5 C.

a-{4- [0& (3,5 dicarbomethoxyphenoxy acetrzmida] benzoyl}-2-octdrlecyloxyacetanilide.-A solution of 34 g. (0.l11+mole) -ofu-(3,S-dicarbomethbxyphenoxy)-acetyl chloride in 200 ml. of dry acetonitrile was added with good stirringover a period of 15 minutes to a reiiuxing solution of 58.0 g. (0.111 mole) of a-(4-aminobenzoyl)- 2 o ctadecyloxyacetanilide--in 500 m1. of dry acetonitrile. Boiliiig' was continued for twohour's. The mixture was cooled and filtered. The solid was recrystallized from acetic acid; yield 620g; (82%), M. P. 153-5 C. The melting point was raised to 157-8" C. after one more crystallization from acetic acid (with Norite).

Exam le 7 Coupler No. VILis prepared as follows: 2

a-benzbyl-4-I2-(2,4-di tertl aniylphenoxy) 5 2,441.

carbomethoxymethoxybenzamido) benzamido] 2 methoxyacIaniZz'deL -A solution or a-benzo 1i-4tzzA di-tit amylphenoxy)-5-aminobenzamido] 2 methoxyacetaiii lide" (see below) in acetonitrile (3.18 g. (0.005 mole) of amine in 10 ml of solvent) was added to a solution of 2,4-dicarbomethoxymethoxybenzoyl chloride (prepared from 1.5 g. (0.005 mole) of theacid and excess thion'yl chloride) in 10 ml. of the same solvent. was boiled for one hour. The yellow-orange solution was drowned in water with good stirring. The solid (3:5 g.) was filtered, washed with water and recrystallized twice from 10 parts ,ofmethanol. The: pure material melted at 173-5 C.

Example 8 Coupler No. VIII is prepared as follows: oz-ben'zO'yl-4[2-(2.4-di-teit.-mfiylphenoay) 5' an'iifio benzamido]-2 methoxyacetanilide hydrochloride.-A mix ture of 6.7 g. (0.01 mole) of a-benzoyl-4[2 (2,4-di-tertamylphenoxy)-5-nitrobenzamido]' 2 methoxyacetani lide, 30 ml. of% ethanol, 20 m1. of water and140'm l. of glacial acetic acid was heated to the boiling point. To the solution was added 6.7 g. of powdered iron, and boiling was continued for 30minutes. The hot mixture was filtered and ml. of 50:50 water-concentrated hydrochloric acid was added to the filtrate. The mixture was cooled and the product filtered and washed with dilute hydrochloric acid; yield 6.0 g. (89%).

a-Benzoyl-4-[2-(2,4-di-tert.-amylphenoxy) 5 (3,5-dicarbo methoxyphenylcarbrzmylvdleramido) benzamid'oJ 2-methoxyaceranilide.--A mixture of 6 g. (0.0089 mole) of a-benzoyl-4-[2-(2,4-di tert.-amylphenoxy) 5 amino benzamido]-2-methoxyacetanilide and 1.8 g. (0.018 n 1ole) ofarihydrous sodium acetate in 50 ml. of glacial acetic acid was stirred at room temperature for 30 minutes. To the mixture was added3.2 grams (0.009mole) of lit-(3,5- dicarbomethoxyphenylcarbamyl)valeryl chloride (U. S; Patent 2,688,544). The reaction mixture was stirred overnight'at room temperature, then drowned inwate'r. The tan solid was dissolved in hot methanol and drowned out again. The product was washed with water and dried; yield 8.0 g. (94%). Analysis.- Calcd for Cs5H N O C, 69.2; H, 6.5; N, 5.9. Found: C, 69.4; H, 6.4; N, 6.1".

Example 9 o-anisidine, 0.2 g. of anhydrous sodium acetatc and225 ml. of xylene was heated under a steam-heateddistillation columnfor 1% hours; as the ethanol-toluene a'zeotrope was distilled. Fifteen milliliters of solvent were distilled off and the distillant was filtered. Most of the xylene was distilledin vacuo from the filtrate, and the residue was treated with hexane. The solid was filtered and crystallized twice from acetonitrile. The yield of productwas 7 g., M1 P. 166-7 C.

a -{4-[2-(2,4 di tert.-amylphenoxy)-5-aniinbbehzmizido] benzoyl} 2-methtoxyactdnilide.A mixture of 3 g. of a {4 [2-(2,4-di tert.-amylphenoxy)-5-nitrobenzamido]benzoyl}-2-methoxyacetanilide, .5 g. of Raney nickel catalyst, .1 g. of sodium carbonate and 100 ml. of'absoluteethanol was shaken underhydr'ogen at3 atmospheres pressure over a period of8hours. To the reaction-mix- The mixture" '11 noxy)acety1 chloride, 0.2 m1. of- N,N-diethylani1ine and 100 ml. of acetone was heated at the boiling point for onehour. After cooling, it was poured onto 300 g. of ice containing 2 ml. of concentrated hydrochloric acid. The solid was filtered, washed with water, and dried. The white solid was recrystallized from 25 ml. of ethanol; yield 0.7 g. (78%), M. P. 150-3" C. The melting point was unchanged after another crystallization from the same solvent.

Compounds X to XIII can be prepared in the manner of the above examples and will be found to exhibit physical and chemical properties similar to Compounds I to IX.

Example 10 Compound XIV, (oz-{3-Ea-(ZA-di-t-amylphenoxy)butyramido]benzoyl}-2-methoxyacetanilide), is prepared as follows:

A slurry of 56.8 g. of u-(3-aminobenzoyl)-2-methoxyacetanilide in 250 cc. of glacial acetic acid and 25 cc. of water was heated until complete solution occurred (ca. 70 C.). To this solution was added 745 g. of (IL-(2,4- di-tert-amylphenoxy) butyryl chloride all at once with vigorous stirring. After several moments, a solution of 18 g. of sodium acetate in 40 cc. of water was added and stirring continued for two hours without heating. The solution was poured into two liters of ice water, and the resulting solid was filtered. After drying, the solid (106 g.) was purified by recrystallization from ligroin. 52 grams of a white solid melting at 105 C. was obtained.

The isomeric Compound XV, (a-{3-[a-(2,4-di-n-amylphenoxy)butyramido] -benzoyl}- 2 methoxyacetanilide) was prepared in the same manner except using 2,4-di-namylphenol instead of 2,4-di-tert-amylphenol and was a white solid having a M..P. of 80 C.

Compounds XIV and XV are particularly valuable since they have lower melting points than, e. g., Compound IV which facilitates the incorporation of the compounds into gelatin emulsions by means of coupler solvents.

The coupler compounds of the invention can be incorporated into silver halide emulsion layers by use of oily coupler solvents as described in the Mannes and Godowsky U. S. Patent 2,304,940, December 15, 1942, and the Jelley and Vittum U. S. Patent 2,322,027, June 15, 1943. However, coupler compounds such as VI to IX containing terminal ester groups can also be hydrolyzed with alkali and when dissolved in aqueous alkaline solution can be incorporated directly into a silver halide emulsion. V

The following example illustrates the use of the coupler Compound IV in an emulsion:

0.6 gram of coupler IV is dissolved in a mixture of 0.3 gram of di-n-butyl phthalate and 2.5 ml. of ethyl acetate by heating with stirring. This solution is mixed with 17.7 ml. of 10% gelatin solution containing 2 ml. of 5% Alkanol B. The mixture is put through a colloid mill four times to eifect dispersion. Fourteen ml. of

. water is used to rinse out the colloid mill and this is added to the dispersion. The dispersion is then chilled and allowed to set. It is then shredded and dried on a stainless steel screen to remove the water and the ethyl acetate. The dried dispersion is then added to 33 ml. of water and allowed to soak for 20 minutes. The mixture is then warmed to 40 C. to melt the gelatin. The melted dispersion is mixed with 8.5 ml. of a sensitive silver halide emulsion and the resulting mixture is coated in the normal manner upon a film base support.

The resulting film is then exposed under an image and developed in a color developing composition as follows:

Grams 2-amino-5-diethy1amino toluene I-I-Cl 2 Sodium sulfite (anhydrous) 2 Sodium carbonate (anhydrous) 20 Potassium bromide 1 Water to 1 liter.

The result is to obtain a silver and yellow dye image in the emulsion layer from which the silver image can be removed by well-known methods. The dye image thus obtained has light absorption properties similar to that obtained from compound 3 (Compound HI of Example 3) as shown in the drawing. Similar results are obtained when the other couplers of the invention are incorporated into silver halide emulsion layers and developed by means of p-phenylenediamine developer compositions. In the development of exposed photographic silver halide emulsion layers using the couplers of our invention, any color-forming developer containing a primary amino group may be used. These include developers having two primary amino groups as well as those having one of the amino groups substituted or having substituents in the ring, such as the alkyl phenylene diamines. These compounds are usually used in the salt form, such as the hydrochloride or the sulfate which are more'stable than the amines themselves. The suitable compounds are diethyl-p-phenylenediamine hydrochlo-' ride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride and 2-amino- S-diethylaminotoluene hydrochloride. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these developers have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color-forming compounds to form a dye image.

As will be apparent, the coupler compounds of the invention find greatest use in the yellow image-forming layer of multi-layer color films. As such, emulsion layers containing the couplers contain as the emulsion vehicle gelatin or other water-permeable organic colloids such as albumin, partially hydrolyzed cellulose esters and partially hydrolyzed polyvinyl esters, polyvinyl alcohol, etc. The carrier may be supported by a transparent medium such as glass, a cellulose ester or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or as one of a number of superposed layers on one or both sides of the support. The superposed layers may be diiferentially sensitized as is conventional in color photography.

What we claim is:

1. A photographic silver halide emulsion containing a coupler compound having the general formula -o oomo 01mg -coonio 01mg wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group GrHu wherein R represents a member of the class consisting of a hydrogen atom and an alkyl group of from 1 to 4 carbon atoms.

3. A photographic silver halide emulsion containing a coupler compound having the general formula Qoocmoonrr Ocoomo 01mg wherein R represents an alkyl group of from 1 to 20 carbon atoms and Y represents the group -NH0 0 duo-3342a" (t) lHnG) wherein R represents an alkyl group of from 1 to 4 carbon atoms.

5. A photographic silver halide emulsion containing a coupler compound having the general formula wherein R represents an alkyl group of from 1 to 20 carbon atoms and X represents the group R! NHCO4JHO CsH1r(t) CaHn(t) wherein R represents an alkyl group of from 1 to 4 carbon atoms. a 1

6. A photographic silver halide emulsion containing the coupler compound 4-benz0ylacetamido-3-methoxy- (2',4-di-tert-amylphenoxy) -acetanilide.

7. A photographic silver halide emulsion containing the coupler compound tat-{3-[ow(2,4-di-n-amylphenoxy) butyramido]-benzoyl}-2-methoxyacetani1ide.

8. A photographic silver halide emulsion containing the coupler compound 3-benzoylacetamino-4-methoxy- (Z',4'-di-tert-amylphenoxy) -acetanilide.

9. A photographic silver halide emulsion containing the coupler compound {3-[w(2,4,-di-tert-amylphenoxy) acetamido] -b enz oyl}-2-methoxyacetanilide.

10. A photographic silver halide emulsion containing the coupler compound a-{3-[a-(2,4-di-tert-amylphenoxy) butyramido]-benzoyl}-2-methoxyacetanilide.

References Cited in the file of this patent UNITED STATES PATENTS 2,678,882 Barr et al May 18, 1954 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COUPLER COMPOUND HAVING THE GENERAL FORMULA 